(NHC)Cu-Catalyzed Mild C–H Amidation of (Hetero)arenes with Deprotectable Carbamates: Scope and Mechanistic Studies

Primary arylamines are an important unit broadly found in synthetic, biological, and materials science. Herein we describe the development of a (NHC)Cu system that mediates a direct C–H amidation of (hetero)­arenes by using N-chlorocarbamates or their sodio derivatives as the practical amino sources...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2016-09, Vol.138 (38), p.12605-12614
Main Authors: Xie, Weilong, Yoon, Jung Hee, Chang, Sukbok
Format: Article
Language:English
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Summary:Primary arylamines are an important unit broadly found in synthetic, biological, and materials science. Herein we describe the development of a (NHC)Cu system that mediates a direct C–H amidation of (hetero)­arenes by using N-chlorocarbamates or their sodio derivatives as the practical amino sources. A facile stoichiometric reaction of reactive copper-aryl intermediates with the amidating reagent led us to isolate key copper arylcarbamate species with the formation of a C–N bond. The use of t BuONa base made this transformation catalytic under mild conditions. The present (NHC)­Cu-catalyzed C–H amidation works efficiently and selectively on a large scale over a range of arenes including polyfluorobenzenes, azoles, and quinoline N-oxides. Deprotection of the newly installed carbamate groups such as Boc and Cbz was readily performed to afford the corresponding primary arylamines.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b07486